火炸药学报

为了得到性能优良的含能材料,以3,5-二氨基-1,2,4三唑为原料,经重氮化、还原反应得到3-肼基-5-氨基-1H-1,2,4-三唑盐酸盐(化合物1),化合物1和硝酸银通过复分解反应制备一种新型含能离子盐3-肼基-5-氨基-1H-1,2,4-三唑硝酸盐(化合物2); 通过红外光谱、核磁共振谱、质谱、元素分析和X-射线单晶衍射分析等对化合物2进行结构表征; 利用差示扫描量热仪(DSC)和热重分析仪(TG)研究了其热分解过程; 采用Crystal Explorer 17.5 软件计算了化合物2晶体中的氢键对其分子间相互作用力的贡献,并研究了其爆轰与安全性能。结果表明,化合物2属于单斜晶系,空间群为P2/n,晶胞参数a=6.9296Å、b=9.9082Å、c=13.3696Å、α=90.00°、β=103.51(2)°、γ=90.00°、V= 892.54(11)Å3,其热分解温度为189.7℃,表现出良好的热稳定性; 同时化合物2具有优异的爆轰性能和较低的感度,其爆速和爆压分别为8673m/s和32.5GPa,摩擦感度和撞击感度分别为112N和25J。

To obtain high-performance energetic materials, 3,5-diamino-1,2,4-triazole was utilized as a raw material to synthesize 3-hydrazinyl-5-amino-1H-1,2,4-triazolium dihydrochloride(compound 1)through diazotization and reduction reactions. A novel energetic ionic salt, 3-hydrazinyl-5-amino-1H-1,2,4-triazolium dinitrate(compound 2), was prepared by the metathesis reaction of compound 1 with silver nitrate. The structure of compound 2 was characterized using various techniques including FTIR, NMR, mass spectrometry, elemental analysis, and single-crystal X-ray diffraction. Thermal decomposition of compound 2 was studied by DSC and TG. The contribution of hydrogen bonding to the intermolecular interactions in the crystal of compound 2 was calculated using Crystal Explorer software. The detonation and safety properties of compound 2 were also investigated. The results show that compound 2 belongs to monoclinic crystal system with space group P2/n and cell parameters a=6.9296Å,b=9.9082Å,c=13.3696Å,α=90.00°,β=103.51(2)°,γ=90.00°,V=892.54(11)Å3. It exhibits excellent thermal stability with a thermal decomposition temperature of 189.7℃. Furthermore, compound 2 demonstrates outstanding detonation performance and low sensitivity, with detonation velocity and pressure values of 8673m/s and 32.5GPa, respectively. The friction sensitivity and impact sensitivity are 112N and 25J, respectively.

引言
1 实验
2 结果与讨论
3 结论

图1 3-肼基-5-氨基-1H-1,2,4-三唑硝酸盐的合成路线<br/>Fig.1 Synthetic route of 3-Hydrazinium-5-amino-1H-1,2,4-triazolium dinitrate

图1 3-肼基-5-氨基-1H-1,2,4-三唑硝酸盐的合成路线
Fig.1 Synthetic route of 3-Hydrazinium-5-amino-1H-1,2,4-triazolium dinitrate

表1 化合物2的晶体结构数据及精修参数<br/>Table 1 Crystallographic data and structure refinement parameters for compound 2

表1 化合物2的晶体结构数据及精修参数
Table 1 Crystallographic data and structure refinement parameters for compound 2

表2 化合物2的部分键长<br/>Table 2 Selected bond lengths of compound 2

表2 化合物2的部分键长
Table 2 Selected bond lengths of compound 2

表3 化合物2的部分键角<br/>Table 3 Selected bond angles of compound 2

表3 化合物2的部分键角
Table 3 Selected bond angles of compound 2

表4 化合物2氢键的键长和键角<br/>Table 4 Hydrogen-bonding geometry of compound 2

表4 化合物2氢键的键长和键角
Table 4 Hydrogen-bonding geometry of compound 2

图2 化合物2的晶体结构、氢键和晶胞堆积图<br/>Fig.2 Crystal structure, hydrogen bond and crystal packing diagram of compound 2

图2 化合物2的晶体结构、氢键和晶胞堆积图
Fig.2 Crystal structure, hydrogen bond and crystal packing diagram of compound 2

图3 化合物2的Hirshfeld表面、二维指纹图和原子间相互作用的比例<br/>Fig.3 Hirshfeld surface, 2D fingerprint plot in crystal stacking and pie graph for individual atomic contact percentage of compound 2

图3 化合物2的Hirshfeld表面、二维指纹图和原子间相互作用的比例
Fig.3 Hirshfeld surface, 2D fingerprint plot in crystal stacking and pie graph for individual atomic contact percentage of compound 2

图4 化合物2的TG-DSC曲线<br/>Fig.4 TG-DSC curves of compound 2

图4 化合物2的TG-DSC曲线
Fig.4 TG-DSC curves of compound 2

表5 化合物2与TATB、RDX 的性能对比<br/>Table 5 The energetic properties of compound 2 compared with TATB and RDX

表5 化合物2与TATB、RDX 的性能对比
Table 5 The energetic properties of compound 2 compared with TATB and RDX

[1] SOHAN L, STAPLES R J, SHREEVE J M, et al. Design and synthesis of phenylene-bridged isoxazole and tetrazole-1-ol based energetic materials of low sensitivity[J]. Dalton Transactions, 2023, 52(11): 3449-3457.
[2]YANG Z L, WU Y M, HE P, et al. Synthesis and characterization of promising insensitive energetic salts based on 3-amino-5-hydrazinopyrazole[J]. Dalton Transactions, 2021, 50(21): 7456-7463.
[3]TANG Y, YIN Z, CHINNAM A K, et al. A duo and a trio of triazoles as very thermostable and insensitive energetic materials[J]. Inorganic Chemistry, 2020, 59(23): 17766-17774.
[4]KLAPOTKE T M,KRUMM B,UNGER C C.Energe-tic metal and nitrogen-rich salts of the pentaerythri-tol tetranitrate analogue pentaerythritol tetranitrocar-bamate[J]. Inorganic Chemistry, 2019, 58(4): 2881-2887.
[5]GUO Z, WANG Y, LIU X, et al. Auxiliary ligand-directed synthesis of 3D energetic coordination polymer from discrete complex: enhanced energy density, thermal stability and energy performance[J]. Crystengcomm, 2019, 21(3): 462-469.
[6]张倩, 段秉蕙, 谭博军, 等. 4,8-二(2,4,6-三硝基-3,5-二氨基苯基)双呋咱并吡嗪的合成与性能[J]. 含能材料, 2023, 31(2): 107-113.

Chinese Journal of Energetic Materials

[7]WANG T W, LU Z J, YI Z X, et al. Preparation of multi-functional type coordination compounds: spanning the quantitative restriction of oxidizing groups[J]. Inorganic Chemistry Frontiers, 2023, 10(5): 1475-1484.

Chinese Journal of Energetic Materials

[9]ZHANG Z B, ZHANG J G. 1-Amine-1,2,3-triazolium salts with oxidizing anions: a new family of energetic materials with good performance[J]. Journal of Molecular Structure, 2018, 1158: 88-95.
[10]SHREEVE J M, YIN P, YU Q, et al. Taming of tetranitroethane: a promising precursor for high performance energetic ingredients[J]. Journal of Materials Chemistry A, 2018, 6(32): 15815-15820.
[11]刘亚静, 刘浩然, 葛瑞荣, 等. 5,5'-肼基双四唑二羟胺盐的合成与性能[J]. 火炸药学报, 2022, 45(5): 651-657.